2-naphthol, Reimer-Tiemann reaction

The starting material for the 1,2-disubstituted tetrahydro-naphthalenes was 5,6,7,8-tetrahydro-2-naphthol. This compound was converted in low yield to the known Via by the Reimer-Tiemann reaction. VI6 and Vic both were prepared from 1-bromo-2-methoxy-5,6,7,8-tetrahydronaphthalene. Although VI6 was prepared according to the method of O Farrell et al. [3], we obtained a much higher yield,... 

Eydroxy-5,6,7,8-tetrahydro-l-napMhaldehyde was prepared [7] by the Reimer-Tiemann reaction cn 5,6,7,8-tetrahydro- 2-naphthol. Three recrystallizations from aqueous alcohol afforded a very low yield of pure aldehyde, m.p. 86-8-87-8° (spectral sample) lit. m.p. 86-87° [7J. 

Today an unequivocal determination of substituent positions on a phenol or naphthol or hydroxyaldehyde by infrared and NMR spectroscopy is usually straightforward and should always be performed routinely the major or most easily isolated product is sometimes not the expected one For example, the most easily isolated product (the first to crystallize) from a Reimer-Tiemann reaction of 3-chlorophenol is 6-chlorosalicylaldehyde, and not the 4-chloro isomer, which is the major product. 

Hydroxy-1-naphthaldehyde has been prepared from /3-naphthol, zinc chloride, and hydrogen cyanide 1 from /3-naphthol, zinc cyanide, and anhydrous hydrogen chloride 2 and from /3-naphthol, chloroform, and sodium hydroxide (Reimer-Tiemann reaction).3... 

It is convenient to discuss the Reimer-Tiemann reaction in terms of its normal and abnormal versions. The normal reaction, discovered in 1876 by Reimer, consists of the treatment of a phenol or naphthol with chloroform in the presence of an alkali metal hydroxide solution (see equations 1 and 2), and results... 

In addition to phenols, naphthols, their alkyl derivatives and the heterocyclic compounds mentioned above, a large variety of substituted monocyclic as well as condensed phenols have been subjected to the Reimer-Tiemann reaction. Although with a few exceptions the yields are only moderate, the facile reaction conditions, at least on a laboratory scale, have assured the reaction a permanent place among the variety of methods by which an aldehyde group can be attached to an aromatic nucleus. For example, phenolphthalein (1) has been formylated under standard Reimer-Tiemann conditions by van Kampen to yield the o-hydroxy aldehyde in 59% yield (equation 5)."... 

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